Process for manufacture of a porous polymer by use of a porogen

ABSTRACT

PCT No. PCT/EP97/01409 Sec. 371 Date May 10, 1999 Sec. 102(e) Date May 10, 1999 PCT Filed Mar. 20, 1997 PCT Pub. No. WO97/35905 PCT Pub. Date Oct. 2, 1997The invention is directed to a process for producing a porous polymer comprising the steps of: (1) dispersing a porogen in a continuous monomer component phase wherein said continuous monomer component phase comprises at least one monomer having at least one perfluoropolyether unit and wherein said porogen is an optionally substituted poly(alkylene)glycol; (2) thereafter polymerising the continuous monomer phase; and (3) removing the porogen from the porous polymer.

The present invention relates to a process for producing porous polymers, in particular to a process for polymerising or copolymerising monomers incorporating perfluoropolyethers to form porous polymers and to porous polymers comprising perfluoropolyethers obtained according to said process.

In many applications it has been found advantageous for polymers to be porous. The degree of porosity required depends on the application. For example, membrane filtration depends on the use of microporous polymers to effect separations of various materials. Also macroporous sheets of chemically resistant polymers find extensive use as cell dividers in cells for electrolysis or electricity storage.

Pores may be formed in the polymer during the process of manufacturing an article of the desired shape or may be formed in the article after manufacture. There are a variety of methods known in the art for the introduction of porosity into synthetic polymers, such as those described in WO 90/07575, WO 91/07687, U.S. Pat. No. 5,244,799, U.S. Pat. No. 5,238,613, U.S. Pat. No. 4,799,931. Some rely on a drilling or etching process after the polymer has been formed. Thus, high energy particles or electromagnetic radiation, such as that emitted from lasers, have been used as described in WO91/07687. These processes are generally labour intensive and time consuming.

Less commonly, the porosity may be an inherent property of the polymer and the porosity maintained as the polymer is formed into the desired shape for a particular application. It is particularly advantageous for the porosity to be introduced during the polymer forming steps. This is generally economical and, in appropriate cases, good control over the porosity and pore size can be achieved.

Polymers based on perfluoropolyethers, in general, have many unique and desirable properties. These include resistance to fouling by proteinaceous and other materials, outstanding flexibility, transparency, high resistance to temperature extremes, and exceptional chemical and oxidation resistance. These properties would make perfluoropolyether based polymers particularly suitable for a variety of applications and would be particularly suited for use as membranes if methods were available for the economic introduction of porosity. Indeed, there has been a long-felt need for membrane materials with the above attributes. Polytetrafluoroethylene-based (PTFE) membrane materials provide a partial solution to this need. However, unlike perfluoropolyether-based polymers, which can be readily cured and formed into articles by in-situ polymerisation, PTFE-based materials suffer from the disadvantage of being difficult to fabricate and manufacture into articles. In addition, stretching processes such as those described in U.S. Pat. No. 3,953,566 (Gore) give a somewhat limited range of size and shape of the porosities and are difficult to control.

Because of the properties mentioned above perfluoropolyether based polymers are highly desirable materials for contact lenses and other ophthalmic devices (U.S. Pat. No. 4,440,918, U.S. Pat. No. 4,818,801); if such materials could be made porous to allow transfer of tear fluids or nutrients their usefulness would be considerably enhanced.

Despite the obvious potential advantages of these materials, porous perfluoropolyether polymers have not previously been available.

In certain polymers porosity may be an interpenetrating network of holes, closed cells or a combination thereof. This may be achieved by polymerization in the presence of an insoluble material often referred to as a porogen. Subsequent leaching of the porogen gives rise to interstices throughout the formed polymer material. Sodium chloride is one such material that has been used. A disadvantage of this process is the difficulty of stabilising the suspension of porogen in the polymerisation mixture. Unstable suspensions can lead to an inhomogeneous and unacceptable product. In many cases, extensive optimisation of the viscosity of the system and the type of porogen is needed to obtain a satisfactory result. In addition the procedure is limited in terms of the availability of porogens suitable for introducing the desired ranges of pore sizes.

A convenient and versatile method of obtaining porous materials is the polymerisation of co-continuous microemulsions. Microemulsion polymerisation involves the polymerisation of a stable isotropic mixture of an oil phase and a water phase stabilized by surfactants. The oil phase generally contains the polymerisable monomer, which polymerises around either contiguous droplets of the water phase stabilized by surfactants or about a co-continuous water phase. Typically, organic solvents are not used in the water phase.

It will be appreciated that fluorochemicals such as perfluoropolyethers possess unusual characteristics in their interaction with other substances. An unusually low surface energy is one such characteristic. Another characteristic is low solubility in many solvents, especially water. The low surface energy and low propensity to adsorb many common materials is, in part, responsible for their outstanding resistance to fouling and degradation and for the utility of fluoropolymers in non-stick and soiling resistant applications. Another consequence of the low surface energy and solubility of fluorochemicals, is that stable emulsions and microemulsions in aqueous and other common media are very difficult to achieve. For example, standard surfactants well-known in the art are ineffective in stabilising aqueous microemulsions containing perfluoropolyethers. Accordingly, standard procedures for making microemulsions are ineffective for perfluoropolyether-based monomers.

We have now found a reproducable and stable process for the production of porous polymers based on perfluoropolyethers. This enables these highly stable and resistant materials to be utilised in porous form. Accordingly there is provided a process for producing a porous polymer comprising the steps of:

1) dispersing a porogen in a continuous monomer component phase wherein said continuous monomer component phase comprises at least one monomer having at least one perfluoropolyether unit and wherein said porogen is an optionally substituted poly(alkylene)glycol;

2) thereafter polymerising the continuous monomer phase; and

3) removing the porogen from the porous polymer.

The polymerizable component includes at least one macromonomer having at least one perfluoropolyether unit. It will be understood by those skilled in the art that the terms "perfluoropolyether unit" and "PFPE unit" preferably mean the moiety of formula PFPE

    --OCH.sub.2 CF.sub.2 O(CF.sub.2 CF.sub.2 O).sub.x (CF.sub.2 O).sub.y CF.sub.2 CH.sub.2 O--                                     (PFPE)

wherein the CF₂ CF₂ O and CF₂ O units may be randomly distributed or distributed as blocks throughout the chain and wherein x and y may be the same or different such that the molecular weight of the perfluorinated polyether is in the range of from 242 to 4,000.

Preferably x in Formula (PFPE) is in the range of from 0 to 20, more preferably in the range from 8 to 12, and y is in the range from 0 to 25, more preferably in the range from 10 to 14. Even more preferred, x and y in Formula (PFPE) are both different from zero such that x is in the range of from 1 to 20, more preferably in the range from 8 to 12, and y is in the range from 1 to 25, more preferably in the range from 10 to 14.

Preferred macromonomers having at least one perfluoropolyether unit include, but are not limited to, those of formula I, II and III as specified hereinafter:

Macromonomers of formula (I):

    Q--(PFPE--L).sub.n-1 --PFPE--Q                             (I)

macromonomers of formula (II):

    Q--B--(L--B).sub.n --T                                     (II)

and macromonomers of formula (III)

    Q--PFPE--L--M--L--PFPE--Q                                  (III)

wherein in these formulae

Q may be the same or different and is a polymerizable group,

PFPE is a divalent residue of formula (PFPE) as hereinbefore defined,

L is a difunctional linking group;

n is at least 1;

in macromonomers of formula (II) each B may be the same or different and is a difunctional block of molecular weight in the range of from 100 to 4000 and wherein at least one B is a perfluorinated polyether of formula (PFPE); in macromonomers of formula (II) T is a univalent terminal group which is not polymerisable by free radicals but which may contain other functionality; and in macromonomers of formula (III) M is a residue from a difunctional polymer or copolymer comprising silicone repeat units of formula IV having a molecular weight preferably in the range of from 180 to 6000 and end functionality as described below ##STR1## wherein R¹ and R² may be the same or different and are selected from the group consisting of hydrogen, alkyl, aryl, halosubstituted alkyl and the like. R¹ and R² are preferably methyl.

In formulae (I), (II), and (III) it is preferred that n is in the range of from 1 to 5, more preferably n is in the range of from 1 to 3. Macromonomers where n is 1 are particularly preferred.

Q is a polymerizable group which preferably comprises an ethylenically unsaturated moiety which can enter into a free radical polymerization reaction. Preferably Q is a group of the formula A

    P.sub.1 --(Y).sub.m --(R'--X.sub.1).sub.p --               (A)

wherein P₁ is a free-radically-polymerizable group;

Y is --CONHCOO--, --CONHCONH--, --OCONHCO--, --NHCONHCO--, --NHCO--, --CONH--, --NHCONH--, --COO--, --OCO--, --NHCOO-- or --OCONH--;

m and p, independently of one another, are 0 or 1;

R' is a divalent radical of an organic compound having up to 20 carbon atoms;

X₁ is --NHCO--, --CONH--, --NHCONH--, --COO--, --OCO--, --NHCOO-- or --OCONH--.

A free-radically-polymerizable group P₁ is, for example, alkenyl, alkenylaryl or alkenylarylenealkyl having up to 20 carbon atoms. Examples of alkenyl are vinyl, allyl, 1-propen-2-yl, 1-buten-2-, -3- and -4-yl, 2-buten-3-yl, and the isomers of pentenyl, hexenyl, octenyl, decenyl and undecenyl. Examples of alkenylaryl are vinylphenyl, vinylnaphthyl or allylphenyl. An example of alkenylarylenealkyl is o-, m-, or p-vinylbenzyl.

P₁ is preferably alkenyl or alkenylaryl having up to 12 carbon atoms, particularly preferably alkenyl having up to 8 carbon atoms, in particular alkenyl having up to 4 carbon atoms.

Y is preferably --COO--, --OCO--, --NHCONH--, --NHCOO--, --OCONH--, NHCO-- or --CONH--, particularly preferably --COO--, --OCO--, NHCO-- or --CONH--, and in particular, --COO-- or --OCO--.

X, is preferably --NHCONH--, --NHCOO-- or --OCONH--, particularly preferably --NHCOO-- or --OCONH--.

In a preferred embodiment, the indices, m and p, are not simultaneously zero. If p is zero, m is preferably 1.

R' is preferably alkylene, arylene, a saturated bivalent cycloaliphatic group having 6 to 20 carbon atoms, arylenealkylene, alkylenearylene, alkylenearylenealkylene or arylenealkylenearylene.

Preferably, R' is a divalent radical having up to 12 carbon atoms, particularly preferably a divalent radical having up to 8 carbon atoms. In a preferred embodiment, R' is furthermore alkylene or arylene having up to 12 carbon atoms. A particularly preferred embodiment of R' is lower alkylene, in particular lower alkylene having up to 4 carbon atoms.

It is particularly preferred that Q be selected from the group consisting of acryloyl, methacryloyl, styryl, acrylamido, acrylamidoalkyl, urethanemethacrylate or any substituted derivatives thereof. Most preferably Q is a compound of formula A wherein P₁ is alkenyl of up to 4 carbon atoms, Y is --COO--, R' is alkylene of up to 4 carbon atoms, X₁ is --NHCOO-- and m and p are each one.

The linking group L may be the bivalent residue of any difunctional moiety able to react with hydroxyl. Suitable precursors to L are α,ω-diepoxides, α,ω-diisocyanates, α,ω-diisothiocyanates, α,ω-diacylhalides, α,ω-dithioacylhalides, α,ω-dicarboxylic acids, α,ω-dithiocarboxylic acids, α,ω-dianhydrides, α,ω-dithioisocyanates, α,ω-dilactones, α,ω-dialkylesters, α,ω-dihalides, α,ω-dialkylethers, α,ω-dihydroxymethylamides. It is preferred that the linking group be a bivalent residue (--C(O)--NH--R--NH--C(O)--) of a diisocyanate or the corresponding residue of a dithioisocyanate, wherein R is a divalent organic radical having up to 20 carbon atoms.

The divalent radical R is, for example, alkylene, arylene, alkylenearyiene, arylenealkylene or arylenealkylenearylene having up to 20 carbon atoms, a saturated bivalent cycloaliphatic group having 6 to 20 carbon atoms or cycloalkylenealkylenecycloalkylene having 7 to 20 carbon atoms.

In a preferred embodiment, R is alkylene, arylene, alkylenearylene, arylenealkylene or arylenealkylenearylene having up to 14 carbon atoms or a saturated divalent cycloaliphatic group having 6 to 14 carbon atoms. In a particularly preferred embodiment, R is alkylene or arylene having up to 12 carbon atoms or a saturated bivalent cycloaliphatic group having 6 to 14 carbon atoms.

In a preferred embodiment, R is alkylene or arylene having up to 10 carbon atoms or a saturated bivalent cycloaliphatic group having 6 to 10 carbon atoms.

In a particularly preferred meaning, R is a radical derived from a diisocyanate, for example from hexane 1,6-diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate, tetramethylene diisocyanate, phenylene 1,4-diisocyanate, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, m- or p-tetramethylxylene diisocyanate, isophorone diisocyanate or cyclohexane i ,4-diisocyanate.

Aryl is a carbocyclic aromatic radical which is unsubstituted or substituted preferably by lower alkyl or lower alkoxy. Examples are phenyl, tolyl, xylyl, methoxyphenyl, t-butoxyphenyl, naphthyl and phenanthryl.

Arylene is preferably phenylene or naphthylene, which is unsubstituted or substituted by lower alkyl or lower alkoxy, in particular 1,3-phenylene, 1,4-phenylene or methyl-1,4-phenylene, 1,5-naphthylene or 1,8-naphthylene.

A saturated bivalent cycloaliphatic group is preferably cycloalkylene, for example cyclohexylene or cyclohexylene(lower alkylene), for example cyclohexylenemethylene, which is unsubstituted or substituted by one or more lower alkyl groups, for example methyl groups, for example trimethylcyclohexylenemethylene, for example the bivaient isophorone radical.

For the purposes of the present invention, the term "lower" in connection with radicals and compounds, unless defined otherwise, denotes, in particular, radicals or compounds having up to 8 carbon atoms, preferably having up to 4 carbon atoms.

Lower alkyl has, in particular, up to 8 carbon atoms, preferably up to 4 carbon atoms, and is, for example, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, hexyl or isohexyl.

Alkylene has up to 12 carbon atoms and can be straight-chain or branched. Suitable examples are decylene, octylene, hexylene, pentylene, butylene, propylene, ethylene, methylene, 2-propylene, 2-butylene, 3-pentylene, and the like.

Lower alkylene is alkylene having up to 8 carbon atoms, particularly preferably up to 4 carbon atoms. Particularly preferred meanings of lower alkylene are propylene, ethylene and methylene.

The arylene unit in alkylenearylene or arylenealkylene is preferably phenylene, unsubstituted or substituted by lower alkyl or lower alkoxy, and the alkylene unit therein is preferably lower alkylene, such as methylene or ethylene, in particular methylene. These radicals are therefore preferably phenylenemethylene or methylenephenylene.

Lower alkoxy has, in particular, up to 8 carbon atoms, preferably up to 4 carbon atoms, and is, for example, methoxy, ethoxy, propoxy, butoxy, tert-butoxy or hexyloxy.

Arylenealkylenearylene is preferably phenylene(lower alkylene)phenylene having up to 8, in particular up to 4, carbon atoms in the alkylene unit, for example phenyleneethylenephenylene or phenylenemethylenephenylene.

Some examples of preferred diisocyanates from which bivalent residues L are derived include trimethylhexamethylenediisocyanate (TMHMDI), isophorone diisocyanate (IPDI), methylenediphenyl diisocyanate (MDI) and 1,6-hexamethylenediisocyanate (HMDI).

The blocks B may be monomeric, oligomeric or polymeric. The molecular weights and chemical composition of each block B may be the same or different, provided that they fall within the molecular weight range specified above. The blocks B may be hydrophobic or hydrophilic, provided that at least one of the blocks is of formula (PFPE). Other suitable blocks B may be derived from poly(alkylene oxides). When one or more of the blocks B is hydrophilic, these blocks are particularly preferably derived from poly(alkylene oxides), more preferably from poly(lower alkylene oxides), most preferred from the polyethylene glycols. It is most preferred that the B blocks are selected from blocks of formula (PFPE) and poly(alkylene oxides), provided that at least one of the blocks is of formula (PFPE). In two very preferred embodiments of the invention there are two B blocks in a macromonomer of formula 11 which are either both of formula (PFPE), or one of which is of formula (PFPE) while the other is derived from a poly(alkylene oxide), preferably from a poly(lower alkylene oxide), most preferred from polyethylene glycols. "Derived from a poly(alkylene oxide)" in the context of the definition of the B blocks means that such a B block differs from a poly(alkylene oxide) in that the two terminal hydrogens have been abstracted from such poly(alkylene oxide). In order to exemplify this, B denotes, if derived from a polyethylene glycol, --(OCH₂ CH₂)_(a) O-- wherein a is the index indicating the number or repeating ethyleneoxy groups.

The terminal group T is a univalent terminal group which is not polymerizable by free radicals but which may contain other functionality. Preferred terminal groups are hydrogen, alkyl, substituted alkyl, aryl or substituted aryl. More preferred groups T are hydrogen, lower alkyl and phenyl.

Suitable substituents for Q or T may be selected from: alkyl, alkenyl, alkynyl, aryl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenyloxy, aryloxy, haloalkoxy, haloalkenyloxy, haloaryloxy, amino, alkylamino, alkenylamino, alkynylamino, arylamino, acyl, aroyl, alkenylacyl, arylacyl, acylamino, alkylsulphonyloxy, arylsulphenyloxy, heterocyclyl, heterocycyloxy, heterocycylamino, haloheterocyclyl, alkoxycarbonyl, alkylthio, alkylsulphonyl, arylthio, arylsulphonyl, aminosulphonyl, dialkylamino and dialkylsulphonyl, having up to 10 carbon atoms.

The difunctional polymer from which M is derived contains an independently selected terminal functionality at each end which may react with the precursor of the linking group L so that a covalent linkage is formed. The preferred terminal functionality is hydroxyl or amino. Such functionality may be joined to the siloxane units in M by means of an alkylene group or other non-reactive spacer. Preferred terminal moieties are hydroxyalkyl, hydroxyalkoxyalkyl and alkylamino. Especially preferred hydroxyalkyls are hydroxypropyl and hydroxybutyl; especially preferred hydroxyalkoxyalkyls are hydroxyethoxyethyl and hydroxyethoxypropyl. Preferred R¹ and R² groups are methyl.

Preferred M residues in formula III as specified above are of formula B ##STR2## where n is an integer from 5 to 100; Alk is alkylene having up to 20 carbon atoms, uninterrupted or interrupted by oxygen; the radicals R₁, R₂, R₃ and R4, independently of one another, are alkyl, aryl or halosubstituted alkyl; and X₃ is --O-- or --NH--.

In a preferred meaning, n is an integer from 5 to 70, particularly preferably 8 to 50, in particular 10 to 28.

In a preferred meaning, the radicals R₁, R₂, R₃ and R₄ are, independently of one another, lower alkyl having up to 8 carbon atoms, particularly preferably lower alkyl having up to 4 carbon atoms, especially lower alkyl having up to 2 carbon atoms. A further particularly preferred embodiment of R₁, R₂, R₃ and R₄ is methyl.

Alkylene interrupted by oxygen is preferably lower alkylene-oxy-lower alkylene having up to 6 carbons in each of the two lower alkylene moieties, more preferably lower alkylene-oxy-lower alkylene having up to 4 carbons in each of the two lower alkylene moieties, examples being ethylene-oxy-ethylene or ethylene-oxy-propylene.

Halosubstituted alkyl is preferably lower alkyl substituted by one or more, especially up to three, halogens such as fluoro, chloro or bromo, examples being trifluoromethyl, chloromethyl, heptafluorobutyl or bromoethyl.

A preferred macromonomer is of formula I wherein n is in the range of from 2 to 5, L is a bivalent residue (--C(O)--NH--R--NH--C(O)--) of a diisocyanate wherein R is alkylene, arylene, alkylenearylene, arylenealkylene or arylenealkylenearylene having up to 14 carbon atoms or a saturated divatent cycloaliphatic group having 6 to 14 carbon atoms, and Q is a compound of formula A wherein P₁ is alkenyl of up to 4 carbon atoms, Y is --COO--, R' is alkylene of up to 4 carbon atoms, X₁ is --NHCOO-- and m and p are each one.

A preferred macromonomer of formula I is one in which n is in the range of from 2 to 5, L is the bivalent residue derived from trimethylhexamethylene diisocyanate (TMHMDI) and Q is the residue derived from isocyanatoethyl methacrylate.

A preferred embodiment of this invention is directed to a macromonomer of formula 1:

    CH.sub.2 ═C(CH.sub.3)COOC.sub.2 H.sub.4 NHCO--(--PFPE--CONH--R--NHCO--).sub.n-1 --PFPE--CONHC.sub.2 H.sub.4 OCOC(CH.sub.3)═CH.sub.2                               (Formula 1)

wherein PFPE is a perfluorinated polyether of formula (PFPE) as herein defined, wherein x is in the range of from 8 to 10 and y is in the range of from 10 to 14, n>1.0, and R is alkylene or arylene having up to 12 carbon atoms or a saturated bivalent cycloaliphatic group having 6 to 14 carbon atoms.

In a preferred embodiment of the present invention there is provided a macromonomer of formula 2:

    CH.sub.2 ═C(CH.sub.3)COOC.sub.2 H.sub.4 NHCO--(--PFPE--CONH--R--NHCO--).sub.n-1 --PFPE--CONHC.sub.2 H.sub.4 OCOC(CH.sub.3)═CH.sub.2                               (Formula 2)

wherein PFPE is a perfluorinated polyether of formula (PFPE) as herein defined, n>1.0, R is the trimethylhexamethylene component of TMHMDI, and wherein x is in the range of from 8 to 10 and y is in the range of from 10 to 14.

In a preferred embodiment of the present invention there are provided macromonomers of formula II which correspond to formulae 3 to 6

    CH.sub.2 ═C(CH.sub.3)COOC.sub.2 H.sub.4 NHCO--PFPE--CONH--R--NHCO--PFPE--H                        (3)

    CH.sub.2 ═C(CH.sub.3)COOC.sub.2 H.sub.4 NHCO--PEG--CONH--R--NHCO--PFPE--H                         (4)

    CH.sub.2 ═C(CH.sub.3)COOC.sub.2 H.sub.4 NHCO--PFPE--CONH--R--NHCO--PEG--CH.sub.3                  (5)

    CH.sub.2 ═C(CH.sub.3)COOC.sub.2 H.sub.4 NHCO--PFPE--CONH--R--NHCO--PEG--H                         (6)

wherein PFPE is of formula (PFPE) wherein x and y are as defined hereinbefore, R is alkylene, arylene, alkylenearylene, arylenealkylene or arylenealkylenearylene having up to 14 carbon atoms or a saturated divalent cycloaliphatic group having 6 to 14 carbon atoms, and PEG is derived from polyethylene glycol. Preferably PEG has a molecular weight in the range of from 200 to 2000.

In an even more preferred embodiment of the present invention there are provided macromonomers of formulae 7 to 10

    CH.sub.2 ═C(CH.sub.3)COOC.sub.2 H.sub.4 NHCO--PFPE--CONH--R--NHCO--PFPE--H                        (7)

    CH.sub.2 ═C(CH.sub.3)COOC.sub.2 H.sub.4 NHCO--PEG--CONH--R--NHCO--PFPE--H                         (8)

    CH.sub.2 ═C(CH.sub.3)COOC.sub.2 H.sub.4 NHCO--PFPE--CONH--R--NHCO--PEG--CH.sub.3                  (9)

    CH.sub.2 ═C(CH.sub.3)COOC.sub.2 H.sub.4 NHCO--PFPE--CONH--R--NHCO--PEG--H                         (10)

wherein PFPE is of formula (PFPE) wherein x and y are as defined hereinbefore, wherein R is the trimethylhexamethylene component of TMHMDI, and PEG is derived from polyethylene glycol. Preferably PEG has a molecular weight in the range of from 200 to 2000. It is also preferred in this embodiment that x is 10 and y is 12.

A preferred macromonomer of formula III is one in which the molecular weight of the perfluorinated polyether is in the range of from 800 to 4,000, L is the bivalent residue derived from trimethylhexamethylene diisocyanate (TMHMDI) and Q is the residue derived from isocyanatoethyl methacrylate. It is particularly preferred that the molecular weight of the perfluorinated polyether is about 2,000 and the molecular weight of M is about 1,000.

A preferred macromonomer of the present invention is of formula 11:

    CH.sub.2 ═C(CH.sub.3)--COO--C.sub.2 H.sub.4 --NHCO--PFPE--CONH--R--NHCO--OCH.sub.2 CH.sub.2 CH.sub.2 --Si(CH.sub.3).sub.2 --(OSi(CH.sub.3).sub.2).sub.11 --CH.sub.2 CH.sub.2 CH.sub.2 O--CONH--R--NHCO--PFPE--CONH--C.sub.2 H.sub.4 --OCO--C(CH.sub.3)═CH.sub.2                           (11)

wherein PFPE is of formula (PFPE), and R is the trimethyhexamethylene component of TMHMDI (trimethylhexamethylene diisocyanate) and wherein x is 10 and y is 12.

The polymerizable component comprises at least one macromonomer having at least one perfluoropolyether unit. Other comonomers may be used to provide useful properties in the porous polymer such as crosslinking agents and other of the macromonomers described above. Suitable comonomers may also include comonomers comprising one or more ethylenically unsaturated groups which can enter into a reaction to form a copolymer. It is preferred that the ethylenically unsaturated group be selected from the group consisting of acryloyl, methacryloyl, styryl, acrylamido, acrylamidoalkyl, urethanemethacrylate, or any substituted derivatives thereof. Suitable comonomers include fluorine and silicon-containing alkyl acrylates and hydropohilic comonomers, which may be selected from the wide range of materials available to a person skilled in the art, and mixturesthereof. Particularly preferred comonomers include dihydroperfluoroalkyl acrylates, such as dihydroperfluorooctyl acrylate and 1,1-dihydroperfluorobutyl acrylate, trihydroper-fluoroalkyl acrylates, tetrahydroperfluoroalkyl acrylates, tris(trimethylsilyoxy)propyl methacrylate or acrylate, and amine-containing comonomers, such as N,N-dimethylaminoethyl methacrylate, N,N-dimethyl acrylamide and N,N-dimethylaminoethyl-acrylamide. Other suitable comonomers may include a wide variety of macromonomers such as vinyl terminated polymethyl methacrylate oligomers and polydimethylsiloxanes terminated with ethylenically unsaturated groups. Where used it is preferred that the comonomers are present in the polymerization component in an amount of from 1 to 60% by weight of the polymerization component, most preferably 2 to 40%.

Copolymers may be formed from mixtures of macromonomers of formulae (I), (II), and (III), with or without other comonomers. Other macromonomers (monofunctional or difunctional) may also be incorporated with or without further comonomers.

A crosslinking agent such as ethylene glycol dimethyacrylate may optionally be added.

When the polymerizable component comprises ethylenically unsaturated monomers the polymerization may be initiated by ionizing radiation, photochemically or thermally using a free radical initiator. It is preferred to use a free radical initiator such as benzoin methyl ether, Darocur, azobisisobutyronitrile, benzoyl peroxide, peroxydicarbonates and the like. Particularly preferred photochemical free radical initiators are benzoin methyl ether and Darocur 1173 (registered trademark of Ciba-Geigy AG). Free radicals may be formed from the initiator by thermal or photochemical means; redox initiation may also be used.

Porogens for use in the present invention may be selected from the range of optionally substituted (i.e. unsubstituted or substituted) poly(alkylene)glycols, preferably those having up to 7 carbon atoms in each alkylene unit which may be the same or different. Unsubstituted poly(alkylene)glycols are preferred. Preferably the porogen is one or more poly(lower alkylene)glycol, wherein lower alkylene in this context denotes alkylene of up to 6 carbon atoms, preferably up to 4 carbon atoms, in each alkylene unit. We have found polypropylene glycols particularly preferred porogens in the process of the present invention. The porogens may be of varying molecular weight and are preferably less than 4000 in molecular weight, even more preferred less than 1000 in molecular weight. We have found it preferable for the porogen to be liquid at room temperature. Substituted poly(alkylene)glycols are understood to include poly(alkylene)glycols wherein one or two hydroxy groups have been replaced by an ether group, e.g. a lower alkoxy group, or an ester group, e.g. a lower alkylcarbonyloxy group, such that a substituted poly(alkylene)glycol may be preferably represented by a mono-poly(alkylene)glycol-ether, a di-poly(alkylene)glycol-ether, a mono-(poly)alkylene)glycol-ester, a di-poly(alkylene)glycol ester, or a poly(alkylene)glycol-monoether-monoester.

While polypropyleneglycol is particularly preferred, other polyalkylene glycols such as polyethylene glycols may also be used.

The polymerizable component may be mixed with the porogen and other optional components by any convenient means. For example the polymerizable component may be mixed with the porogen and other optional components by shaking or stirring. The order in which the components are added to the mixture is not narrowly critical. The mixture may be in the form of an homogeneous solution or may have the porogen as a distinct phase.

Minor amounts of property modifying components may optionally be added to the mixture before polymerization. For example, solvents may be added. Suitable solvents include short chain alcohols, amines or ethers, as well as ethyl acetate, dimethyl formamide, water and fluorinated alcohols. In most cases such solvents are added to reduce viscosity of the solution or to make the solution easier to dispense, for example into molds.

Surfactants, preferably fluorinated surfactants, may be incorporated into the mixture. The use of surfactants is an efflective means of controlling the size and density of the pores.

Non-ionic surfactants containing fluorine are preferred. Particularly preferred surfactants include commercially available fluorinated surfactants such as Zonyl (DuPont) and Fluorad (3M). Zonyl FS300 (DuPont), which is made of a perfluorinated hydrophobic tail and hydrophilic poly(ethylene oxide) head group, is a particularly preferred surfactant for use in the process of the present invention.

Another type of compound which may act as a surfactant in the context of this invention are macromonomers of formula II as disclosed herein. These compounds are disclosed in more detail in International patent application No. PCT/EP96/01256, the relevant disclosure of which, including the preferences thereof, is incorporated herein.

The mixture may be polymerised by any convenient method generally as described above with reference to the initiation of the polymerizable component. Suitable polymerization conditions will be apparent to those skilled in the art. For example, temperatures may range from -100 to 350° C. and pressures may range from below atmospheric to above atmospheric.

It will be understood that by "a substantial proportion of the porogen remains in the form of a discrete phase" we mean that there is sufficient porogen to form either an interpenetrating network or a dispersion. It will be understood by the person skilled in the art that depending on the polymerization component and the porogen a proportion of porogen may be adsorbed or retained in the polymerization component and eventually in the porous polymer. Typically more than 60% of the porogen is in the form of a discrete phase immediately after polymerization. It is preferred that greater than 80% of the porogen is in the form of a discrete phase, more preferably greater than 95% of the porogen is in the form of a discrete phase.

It is particularly preferred that the porogen forms an interpenetrating network in the polymerization component resulting in the porous polymer having a reticulated porous morphology. The reticulated porous morphology may be an open-cell, sponge-like structure consisting of interconnected polymer globular particles or may have an open-cell structure with an array of interconnected generally spherical pores.

In another preferred embodiment the porous polymer may be in the form of a closed-cell structure with discrete pores dispersed throughout the polymer.

The porogen may be removed from the porous polymer by any convenient means. Suitable means for removal of porogen (or solvent) include evaporation, solvent extraction, washing or leaching.

The process of the present invention is useful for generating materials of various pore sizes and morphologies. The upper limit of average pore size of individual pores is about 5 microns, with 100 nanometres being typical, while pores of around 10 nanometres in diameter may also be obtained.

The pores may form an interpenetrating network. It is more useful to characterise these morphologies in terms of permeability to molecules of defined molecular weight. This is described before the examples section.

The morphology and porosity of the porous polymer may be controlled by altering the ratio of the porogen to the polymerizable monomer component. At high ratios of porogen, an open sponge-like structure consisting of interconnected polymer globular particles is obtained. At lower ratios, a reticular network of pores is obtained. At even lower ratios a closed-cell morphology is obtained.

Particularly useful embodiments of the present method have the porogen phase in the form of a continuous interpenetrating network structure which may be readily extracted to leave a porous PFPE material having a reticular network of pores allowing ready passage of fluid and small diameter particles through the porous polymer.

The size and density of the pores may be controlled by the ratio of the poymerizable component to porogen. Minor changes can be effected by the use of surfactants as hereinabove described. The addition of a minor proportion of water also increases porosity.

In another aspect this invention provides a porous perfluoropolyether-containing polymer (homopolymer or copolymer) as described above when made by the process of this invention.

As stated to some extent hereinbefore, comonomers comprising one or more ethylenically unsaturated groups which can enter into a reaction to form a copolymer may be incorporated. It is preferred that the ethylenically unsaturated group be selected from the group consisting of acryloyl, methacryloyl, styryl, acrylamido, acrylamidoalkyl, or urethanemethacrylate, or any substituted derivatives thereof.

A comonomer used in this process may be hydrophilic or hydrophobic or a mixture thereof. Suitable comonomers are, in particular, those which are usually used in the production of contact lenses and biomedical materials. A hydrophobic comonomer is taken to mean a monomer which typically gives a homopolymer which is insoluble in water and can absorb less than 10% by weight of water. Analogously, a hydrophilic comonomer is taken to mean a monomer which typically gives a homopolymer which is soluble in water or can absorb at least 10% by weight of water.

Suitable hydrophobic comonomers are, without limitation thereto, C₁ -C₁₈ alkyl and C₃ -C₁₈ cycloalkyl acrylates and methacrylates, C₃ -C₁₈ alkylacrylamides and -methacrylamides, acrylonitrile, methacrylonitrile, vinyl C₁ -C₁₈ alkanoates, C₂ -C₁₈ alkenes, C₂ -C₁₈ haloalkenes, styrene, (lower alkyl)styrene, lower alkyl vinyl ethers, C₂ -C₁₀ perfluoroalkyl acrylates and methacrylates and correspondingly partially fluorinated acrylates and methacrylates, C₃ -C₁₂ perfluoroalkylethylthiocarbonylaminoethyl acrylates and methacrylates, acryloxy- and methacryloxyalkylsiloxanes, N-vinylcarbazole, C₁ -C₁₂ alkyl esters of maleic acid, fumaric acid, itaconic acid, mesaconic acid and the like.

Preference is given, for example, to acrylonitrile, C₁ -C₄ alkyl esters of vinylically unsaturated carboxylic acids having 3 to 5 carbon atoms or vinyl esters of carboxylic acids having up to 5 carbon atoms.

Examples of suitable hydrophobic comonomers are methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyltoluene, vinyl ethyl ether, perfluorohexylethylthiocarbonylaminoethyl methacrylate, isobornyl methacrylate, trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, hexafluorobutyl methacrylate, tristrimethylsilyloxysilylpropyl methacrylate (hereinafter: Tris methacrylate), tristrimethylsilyloxysilylpropyl acrylate (hereinafter: Tris acrylate), 3-methacryloxy propylpentamethyldisiloxane and bis(methacryloxypropyl)tetramethyidisiloxane.

Preferred examples of hydrophobic comonomers are methyl methacrylate, Tris acrylate, Tris methacrylate and acrylonitrile.

Suitable hydrophilic comonomers are, without this being an exhaustive list, hydroxyl-substituted lower alkyl acrylates and methacrylates, acrylamide, methacrylamide, (lower alkyl)-acrylamides and -methacrylamides, ethoxylated acrylates and methacrylates, hydroxyl-substituted (lower alkyl)acrylamides and -methacrylamides, hydroxyl-substituted lower alkyl vinyl ethers, sodium vinyisulfonate, sodium styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylpyrrole, N-vinyl-2-pyrrolidone, 2-vinyloxazoline, 2-vinyl-4,4'-dialkyloxazolin-5-one, 2- and 4-vinylpyridine, vinylically unsaturated carboxylic acids having a total of 3 to 5 carbon atoms, amino(lower alkyl)- (where the term "amino" also includes quaternary ammonium), mono(lower alkylamino)(lower alkyl) and di(lower alkylamino)(lower alkyl) acrylates and methacrylates, allyl alcohol and the like. Preference is given, for example, to N-vinyl-2-pyrrolidone, acrylamide, methacrylamide, hydroxyl-substituted lower alkyl acrylates and methacrylates, hydroxy-substituted (lower alkyl)acrylamides and -methacrylamides and vinylically unsaturated carboxylic acids having a total of 3 to 5 carbon atoms.

Examples of suitable hydrophilic comonomers are hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate, hydroxypropyl acrylate, trimethylammonium 2-hydroxy propylmethacrylate hydrochloride (Blemer® QA, for example from Nippon Oil), dimethylaminoethyl methacrylate (DMAEMA), dimethylaminoethyl (meth)acrylamide, acrylamide, methacrylamide, N,N-dimethylacrylamide (DMA), allyl alcohol, vinylpyridine, glycerol methacrylate, N-(1,1-dimethyl-3-oxobutyl)acrylamide, N-vinyl-2-pyrrolidone (NVP), acrylic acid, methacrylic acid and the like.

Preferred hydrophilic comonomers are trimethylammonium 2-hydroxy propyimethacrylate hydrochloride, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, trimethylammonium 2-hydroxypropylmethacrylate hydrochloride, N,N-dimethylacrylamide and N-vinyl-2-pyrrolidone.

As stated hereinbefore, suitable comonomers include fluorine- and silicon-containing alkyl acrylates and hydrophilic comonomers, which may be selected from a wide range of materials available, and mixtures thereof. Particularly preferred comonomers include dihydroperfluoroalkyl acrylates, such as dihydroperfluorooctyl acrylate and 1,1-dihydroperfluorobutyl acrylate, trihydroperfluoroalkyl acrylates, tetrahydroperfluoroalkyl acrylates, tris(trimethylsilyloxy)propyl methacrylate or acrylate, and amine-containing comonomers, such as N,N-dimethylaminoethyl methacrylate, N,N-dimethylacrylamide and N,N-dimethyl-aminoethyl-acrylamide. The preferred range for addition of individual comonomers into the formulation is from 0 to 60% by weight and most preferably 0 to 40% by weight of the formulation. Mixtures of macromonomers of formula I, II or III may also be used to make suitable copolymers with or without other comonomers.

A polymer network can, if desired, be reinforced by addition of a crosslinking agent, for example a polyunsaturated crosslinking comonomer. In this case, the term crosslinked polymers is used. The invention, therefore, furthermore relates to a process for producing a crosslinked polymer comprising the product of the polymerization of a macromer of the formula (I), (II), or (III), if desired with at least one vinylic comonomer and with at least one crosslinking comonomer.

Examples of typical crosslinking comonomers are allyl (meth)acrylate, lower alkylene glycol di(meth)acrylate, poly(lower alkylene) glycol di(meth)acrylate, lower alkylene di(meth)acrylate, divinyl ether, divinyl sulfone, di- and trivinylbenzene, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, bisphenol A di(meth)acrylate, methylenebis(meth)acrylamide, triallyl phthalate and diallyl phthalate.

If a crosslinking comonomer is used, the amount used is in the range of from 0.05 to 20% of the expected total weight of polymer, preferably the comonomer is in the range of 0.1 to 10%, and more preferably in the range of 0.1 to 2%.

According to a further aspect of the present invention there is provided an ophthalmic device, preferably a contact lens, and even more preferred a soft contact lens manufactured from the porous polymers or copolymers as hereinbefore described.

Contact lenses, and also soft contact lenses, are polymer disks with surfaces of differing radii of curvature. The radii are selected in combination with the refractive index of the polymer so that the desired optical correction is obtained and the inner surface of the lens matches the contour of wearer's cornea. They are normally sold in sterile saline. Optionally the surface of the lens may be modified by coating using procedures well known to the art, such as plasma polymerisation, glow discharge or grafting of a more hydrophilic polymer.

By way of example, the process can be used in the manufacture of articles, such as ophthalmic devices, preferably contact lenses. In such a case the appropriate quantities of polymerizable monomers, solvent (if required) and photoinitiator are mixed together to form a polymerization mixture. The polymerization mixture is then flushed with nitrogen and the required quantity dispensed into the concave half of a polypropylene mould. The mould is closed and clamped and the assembly is placed into a UV irradiation cabinet equipped with UV lamps. The irradiation is performed for the required time and then the halves of the mould are separated. The polymerized lens is extracted in an appropriate solvent (for example, an isopropyl or tert-butylacetate/fluorinated solvent mixture). The solvent is then extensively exchanged with an alcohol (for example, isopropyl alcohol) and subsequently with saline to yield the product lens.

The polymers produced according to the present invention may be formed into other useful articles using conventional moulding and processing techniques as are well known in the art. Given the visual transparency of the polymers of the present invention, they may find use in tissue culture apparatus, optical instruments, microscope slides and the like.

A further aspect of this invention is the use of the porous perfluoropolyether in film or sheet form as a membrane or a filter. Such porous PFPE film may be laminated with another support film to form a composite. Such applications may involve permeability to gases or liquids.

The porous polymers of the present invention may be suitable, for example, for use in the fields of membrane filters and separation, in the field of industrial biotechnology, and in the biomedical field.

Examples for the field of membrane filters and separation are industrial membranes, e.g. for micro filtration and ultra filtration, for example in the food, dairy, juice, or low alcohol beer industries, waste water treatment, home reverse osmosis, or membrane distillation using osmotic pressure.

Examples for the field of industrial biotechnology are supports for synthetic and biological ligands or receptors for bioreactors and biosensors, sustained release devices for active compounds, or capacitors.

Examples for the biomedical field are ophthalmic devices, e.g. contact lenses or artificial cornea, dialysis and blood filtration, encapsulated biological implants, e.g. pancreatic islets, implanted glucose monitors, drug delivery patches and devices, wound healing and dressing, artificial skin, vascular grafts, regenerative templates or patches for wound healing, (soft) tissue augmentation, percutaneous fixation devices or artificial organs.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.

A generally applicable procedure for handling the porous polymers, once polymerized, is e.g. as follows: The polymers are removed from the mold and placed through a general extraction and drying procedure to remove any unpolymerised components. This procedure consists of a 4 h soaking in a fluorinated solvent (PF5060 from 3M Corporation), then 16 hr immersion in isopropyl acetate and subsequent immersion for 4 h in isopropyl alcohol. After drying in vacuo the polymer takes on a white colour. When the white polymer undergoes a graded solvent change from ethanol, 75% ethanol/water, 50% ethanol/water, 25% ethanol/water, then pure water or saline, it becomes transparent. The graded solvent change has the effect of introducing water into the porous channels of the porous PFPE materials; this occurs despite the very hydrophobic nature of PFPE based materials.

In the examples in this specification Macromonomer (1) is a vinyl terminated perfluorinated macromer of the formula

    CH.sub.2 ═C(CH.sub.3)COOC.sub.2 H.sub.4 NHCO--PFPE--CONHC.sub.2 H.sub.4 OCOC(CH.sub.3)═CH.sub.2

wherein PFPE is the perfluorinated polyether component of 3M Experimental Product L-12875 being a mixture of perfluorinated polyethers of formula:

    --OCH.sub.2 CF.sub.2 O(CF.sub.2 CF.sub.2 O).sub.x (CF.sub.2 O).sub.y CF.sub.2 CH.sub.2 O--

wherein the CF₂ CF₂ O and CF₂ O units may be randomly distributed or distributed as blocks throughout the chain and wherein x is in the range of from 8 to 10 and y is in the range of from 10 to 14.

The present invention is further described in the following non-limiting examples. If not otherwise specified, all parts are by weight. Temperatures are in degrees Celsius. Molecular weights of macromers or polymers are number average molecular weights if not otherwise specified.

The Following Methods are Used:

Water Content Measurement

The % water content (w/w) of the porous polymers was determined by comparing the hydrated and dehydrated weight of the polymers. The polymers were first dried overnight in a vacuum oven (0.1 mmHg) at 37° C. then weighed on cooling. Hydration was achieved via a graded solvent exchange process The dry polymer disks are soaked in the following solutions in turn, spending 1/2 an hour in each solution before the solvent is changed for the next. For every 10 polymer disks 60 ml of solvent was used.

1. 100% Ethanol

2. 75% Ethanol/water

3. 50% Ethanol/water

4. 25% Ethanol/water

5. 100% Water

The polymers are allowed to equilibrate overnight in water or until constant weight--equilibration times for hydrophilic polymers may be longer than 16 h. The hydrated polymers are placed on fine grade lint free Kimwipes paper (Kimberly-Clark) to pat dry the excess surface moisture and finally weighed as the hydrated weight. ##EQU1## Permeability Measurement

Method A

Monitoring permeability by UV spectroscopy Permeant: Bovine Serum Albumin (BSA, Molecular weight=67,000). Concentration of BSA=8 mg/ml in Phosphate buffered saline (PBS), PBS=20 mM Phosphate in 0.2M sodium chloride, pH=7.4.

The porosity of the synthetic polymers was investigated using a static diffusion cell (ie. solutions are not stirred). This method involves fixing one hydrated flat 20 mm diameter polymer disk (see water content measurements for hydration procedure) between two chambers which are separated by a rubber `O` ring with a internal diameter of 7.5 cm. Each chamber holds a volume of approximately 2.2 ml. One chamber contains an 8 mg/ml solution of BSA in PBS while the other chamber is filled with only PBS. At selected time intervals samples were removed from the PBS chamber using a glass pipette and the UV. absorbance of the solution measured at 280 nm (A₂₈₀). This determines whether any BSA had diffused through the polymer disk. A higher absorbance reading points to a higher rate of BSA diffusion and is therefore indicative of a structure with a relatively large pore size and/or a larger pore density.

Method B

A more quantitative measurement of BSA permeability was established using a device in which the flat 20 mm diameter sample was fixed between two chambers in which the BSA/PBS and PBS solutions were being stirred at rates of greater than 200 rpm. The purpose of stirring was to overcome the mass transfer resistance which predominantly exists at the surface boundary layer of a porous material. This method was used to measure the permeability of the polymer disks to glucose, Inulin and I₁₂₅ labelled BSA. The permeability is measured relative to commercial track etched polycarbonate membranes (Trade name of Poretics) with pore sizes of 50 nm and 25 nm.

EXAMPLE 1

The following formulation was placed in polypropylene lens moulds and polymerised for 3 hours over the irradiation generated from a U.V. lamp at a wavelength of 365 nm. All parts are by weight.

    ______________________________________                                         Macromonomer (1)       1.61 parts                                                PPG-725  0.26 parts                                                            Darocur 0.008 parts                                                          ______________________________________                                    

PPG-725 is poly(propylene glycol) of molecular weight 725. The permeability of the lenses to a solution of BSA was monitored by the U.V. spectroscopic technique. After 21 hours the absorbance reading of the initially protein free PBS solution was A₂₈₀ =0.066, this increased to A₂₈₀ =0.117 after 44 hours.

EXAMPLE 2

The following formulation was placed in polypropylene lens moulds (0.2 mm thick, 20 mm diameter) and polymerised for 3 hours over the irradiation generated from a U.V. lamp at a wavelength of 365 nm. All parts are by weight.

    ______________________________________                                                        A (parts)                                                       ______________________________________                                         Macromonomer (1) 0.045                                                           Poly(propylene glycol) 0.28                                                    (Mw = 192)                                                                     Isopropanol 0.10                                                               Darocur 0.007                                                                ______________________________________                                    

The permeability of the lenses to a solution of BSA was monitored by the U.V. spectroscopic technique. After 24 hours the absorbance reading for lens A was A₂₈₀ =0.28. After hydration the water content of lens A was measured to be 31.8% (w/w).

The preparation of porous polymers from formulation A was equally as successful when the isopropanol was replaced with other common organic solvents such as ethanol, ethylacetate and dimethylformamide.

EXAMPLE 3

The following formulations were placed in polypropylene lens moulds (0.2 mm thick, 20 mm diameter) and polymerised for 3 hours over the irradiation generated from a U.V. lamp at a wavelength of 365 nm. All parts are by weight.

    ______________________________________                                                          A    B                                                        ______________________________________                                         Macromonomer (1)   1.014  1.402                                                  PPG-725 0.212 --                                                               Isopropanol 0.306 0.417                                                        Darocur 0.3 0.3                                                              ______________________________________                                    

The permeability of the lenses to a solution of BSA was monitored by the U.V. spectroscopic technique. After 21 hours the absorbance reading for lens A was A₂₈₀ =0.364 and lens B was A₂₈₀ =0.05.

Example B is a control sample which highlights that the protein permeability observed in example A was due to the addition of PPG.

EXAMPLE 4

The following formulation was placed in polypropylene lens moulds (0.2 mm thick, 20 mm diameter) and polymerised for 3 hours over the irradiation generated from a U.V. lamp at a wavelength of 365 nm. All parts are by weight.

    ______________________________________                                                        A                                                               ______________________________________                                         Macromonomer (1) 0.45                                                            PPG-192 0.28                                                                   Isopropanol 0.09                                                               Darocur 0.3                                                                  ______________________________________                                    

The permeability of the lenses to a solution of BSA was monitored by the U.V. spectroscopic technique. After 24 hours the absorbance reading for lens A was A₂₈₀ =0.277. After hydration the water content of lens A was measured to be 32% (w/w).

EXAMPLE 5

The following formulation was placed in polypropylene lens moulds (0.2 mm thick, 20 mm diameter) and polymerised for 3 hours over the irradiation generated from a U.V. lamp at a wavelength of 365 nm. All parts are by weight.

    ______________________________________                                                        A                                                               ______________________________________                                         Macromonomer (1) 0.30                                                            PPG-425 0.18                                                                   Ethanol 0.06                                                                   Darocur 0.3                                                                  ______________________________________                                    

The permeability of the lenses to a solution of BSA was monitored by the U.V. spectroscopic technique. After 24 hours the absorbance reading for lens A was A₂₈₀ =0.210. After hydration the water content of lens A was measured to be 36% (w/w).

EXAMPLE 6

The following formulation was placed in polypropylene lens moulds (0.2 mm thick, 20 mm diameter) and polymerised for 3 hours over the irradiation generated from a U.V. lamp at a wavelength of 365 nm. All parts are by weight.

    ______________________________________                                                        A                                                               ______________________________________                                         Macromonomer (1) 0.30                                                            PPG-425 0.18                                                                   Dimethylformamide 0.10                                                         Darocur 0.3                                                                  ______________________________________                                    

The permeability of the lenses to a solution of BSA was monitored by the U.V. spectroscopic technique. After 24 hours the absorbance reading for lens A was A₂₈₀ =0.17. After hydration the water content of lens A was measured to be 36% (w/w).

EXAMPLE 7

The following formulations were placed in polypropylene lens moulds (0.2 mm thick, 20 mm diameter) and polymerised for 3 hours over the irradiation generated from a U.V. lamp at a wavelength of 365 nm. All parts are by weight.

    ______________________________________                                                          A    B                                                        ______________________________________                                         Macromonomer (1)   0.3    0.3                                                    PPG-425 0.18 0.3                                                               ethyl acetate 0.1 0.1                                                          Darocur 0.3 0.3                                                              ______________________________________                                    

The permeability of the lenses to a solution of BSA was monitored by the U.V. spectroscopic technique. After 24 hours the absorbance reading for lens A was A₂₈₀ =0.22 and lens B was A₂₈₀ =0.46. After hydration the water content of lenses A and B was measured to be 36 and 47% (w/w) respectively.

Note that increasing the level of PPG-425 in formulation B has produced a polymer with a higher water content and a higher permeability to BSA.

EXAMPLE 8

The following formulations were placed in polypropylene lens moulds (0.2 mm thick, 20 mm diameter) and polymerised for 3 hours over the irradiation generated from a U.V. lamp at a wavelength of 365 nm. All parts are by weight.

    ______________________________________                                                          A    B                                                        ______________________________________                                         Macromonomer (1)   0.3    0.3                                                    PPG-425 0.18 0.24                                                              Isopropanol 0.06 0.06                                                          Darocur 0.3 0.3                                                              ______________________________________                                    

The permeability of the lenses to a solution of BSA was monitored by the U.V. spectroscopic technique. After 24 hours the absorbance reading for lens A was A₂₈₀ =0.17 and lens B was A₂₈₀ =0.32. After hydration the water content of lenses A and B was measured to be 35 and 41% (w/w) respectively.

Note that increasing the level of PPG-425 in formulation B has produced a polymer with a higher water content and a higher permeability to BSA.

Those skilled in the art will appreciate that the invention described herein is susceptible to variations and modifications other than those specifically described. It is to be understood that the invention includes all such variations and modifications which fall within the its spirit and scope. 

The claims are as follows:
 1. A process for producing a porous polymer comprising the steps of:1) dispersing a porogen in a continuous monomer component phase wherein said continuous monomer component phase comprises at least one monomer having at least one perfluoropolyether unit and wherein said porogen is an optionally substituted poly(alkylene)glycol; 2) thereafter polymerising the continuous monomer phase; and 3) removing the porogen from the porous polymer.
 2. A process according to claim 1 wherein the porogen is an unsubstituted poly(alkylene)glycol.
 3. A process according to claim 1 wherein the porogen is a polypropylene glycol.
 4. A process according to claim 1 wherein the porogen is a polypropylene glycol with a molecular weight less than
 1000. 